Organic Reactions - Equilibria, Kinetics and Mechanism

Abstract

Part 1 Introduction. Part 2 Nonkinetic method for the elucidation of reaction mechanisms: stoichiometry and reaction mechanisms structure of products structure of intermediates stereochemical experiments isotopic labeling experiments crossover experiments. Part 3 Energetics of chemical reactions: nomenclature of thermodynamic potential functions thermodynamic requirements for chemical reactions kinetic requirements for chemical reactions the principle of microscopic reversibility kinetic and thermodynamic control. Part 4 Kinetics of elementary reactions: basic principles of reaction kinetics the integrated rate equation pseudo-orders of simplified rate equations numerical determination of reaction order and rate constants from experimental data. Part 5 Kinetics of complex reactions: reversible reactions parallel reactions consecutive reactions approximate methods for analyzing complex reactions conclusions examples. Part 6 Theories of chemical reactions: temperature dependence of chemical equilibria temperature dependence of reaction rates collision theory transition-state theory structure of activated complexes entropy of activation enthalpy of activation the isokinetic relationship volume of activation. Part 7 Structure and reactivity relationships: the Hammett equation the linear free-enthalpy relationship the application of Hammett equation to multistep reactions the sigma(+), sigma(-), and sigma(0) substituent constants the Yukawa-Tsuso equation separation of inductive and resonance effects separation of electronic and steric effects. Part 8 Isotope effects: isotope effects on equilibria theory of kinetic isotope effect primary kinetic isotope effect secondary kinetic isotope effects solvent isotope effect. Part 9 Environmental effects: the structure of liquids solvation solvent effects in chemical equilibria solvent effect in chemical kinetics solvent effect on reaction rates specific solvation effects on reaction rates empirical solvent-polarity parameters salt effects. Part 10 Acids, bases, electrophiles and nucleophiles: strengths of Bronsted acids and bases structural effects on Bronsted acidity and basicity solvent effect on acidity and basicity acidity of solvents and acidity functions very weak acids superacids Lewis acids and Lewis bases nucleophiles and electrophiles. Part 11 Homogeneous catalysis: acid-base catalysis rates of proton-transfer reactions Bronsted's law of catalysis reactions in strongly acidic media nucleophilic catalysis electrophilic catalysis neighboring group participation and intramolecular catalysis micellar catalysis enzymic catalysis.